WO2013007819A1 - Method for producing water-absorbing polymer particles having a high swelling speed - Google Patents

Method for producing water-absorbing polymer particles having a high swelling speed Download PDF

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WO2013007819A1
WO2013007819A1 PCT/EP2012/063801 EP2012063801W WO2013007819A1 WO 2013007819 A1 WO2013007819 A1 WO 2013007819A1 EP 2012063801 W EP2012063801 W EP 2012063801W WO 2013007819 A1 WO2013007819 A1 WO 2013007819A1
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example
water
polymer particles
preferably
monomer
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PCT/EP2012/063801
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German (de)
French (fr)
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Markus Braun
Matthias Weismantel
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Basf Se
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • C08F2/24Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26Emulsion polymerisation with the aid of emulsifying agents anionic
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/60Liquid-swellable gel-forming materials, e.g. super-absorbents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04Acids; Metal salts or ammonium salts thereof
    • C08F220/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/1006Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylat

Abstract

The invention relates to a method for producing water-absorbing polymer particles having a high swelling speed by polymerising a monomer solution or monomer suspension containing an ethylenically unsaturated monomer bearing an acid group, a cross-linking agent, an initiator, and an ethylenically unsaturated ionic surfactant.

Description

A process for producing water-absorbing polymeric particles with high swell

description

The present invention relates to a process for producing water-absorbing polymeric particles with high swell by polymerizing a monomer solution or suspension comprising one ethylenically unsaturated acid-functional monomer, a crosslinker, an initiator and an ethylenically unsaturated, ionic surfactant.

Water-absorbing polymer particles are used to produce diapers, tampons, sanitary napkins and other hygiene articles, but also used as water-retaining agents in market gardening. The water-absorbing polymer particles are also referred to as superabsorbents.

The production of water-absorbing polymer particles is described in the monograph "Modern Supe- rabsorbent Polymer Technology", FL Buchholz and AT. Graham, Wiley-VCH, 1998, pages 71 to 103. described. The properties of water-absorbing polymer particles can be adjusted, for example via the amount of crosslinker used. With increasing amount of crosslinker the cen- decreases rifugenretentionskapazität (CRC) and the absorption under a pressure of 21, 0 g / cm 2 (AUL0.3 psi) passes through a maximum. To improve the application properties, such as permeability of the swollen gel bed (SFC) in the diaper and Absorbency under a pressure of 49.2 g / cm 2

(AUL0.7 psi) are crosslinked water-absorbing polymer particles are generally oberflächennach-. Characterized the degree of crosslinking of the particle surface area increases, whereby the absorbency (CRC) can be at least partially decoupled under a pressure of 49.2 g / cm 2 (AUL0.7 psi), and centrifuge retention capacity. This surface can be performed in aqueous gel phase. Preferably, however, dried, ground and screened polymer particles (base polymer) are coated with a postcrosslinker on the surface and surface thermally surface postcrosslinked. Useful crosslinkers are compounds which can form covalent bonds with at least two carboxylate groups of the water-absorbing polymer particles.

The earlier application with the application number PCT / EP201 1/0055761 teaches the use of comonomers to increase the swell. Object of the present invention to provide an improved process for producing water-absorbing polymer particles, in particular of water-absorbing polymeric particles with high swell rate. The object is achieved by a process for producing water-absorbing polymer particles by polymerizing a monomer solution or suspension comprising a) an ethylenically unsaturated acid-functional monomer which may be at least partially neutralized,

b) at least one crosslinker,

c) at least one initiator,

d) optionally, a monomer copolymerizable with the above-mentioned under a) monomers ethylenically unsaturated monomer and

e) optionally one or more water-soluble polymers, characterized in that the monomer solution or suspension containing at least one ethylenically unsaturated nonionic surfactant.

The used according to invention ethylenically unsaturated, ionic surfactants are interfacially active compounds which lower the surface tension of water, preferably as below 70mN / m, more preferably below 68 mN / m, more preferably below 67 mN / m, measured at 23 ° C 0,103gew .-% solution in water.

Ethylenically unsaturated ionic surfactants preferably have an ethylenically unsaturated group, a non-polar spacer and an ionic end group, with anionic end groups are preferred. Suitable ethylenically unsaturated groups include allyl ether, vinyl ether, acrylic ester and methacrylic ester groups. A suitable non-polar spacer is, for example, a polypropylene glycol group. Suitable ionic end groups are for example, quaternary amine, phosphate and sulfate groups.

Particularly suitable ethylenically unsaturated, ionic surfactants are compounds of general formula (I)

Figure imgf000003_0001
wherein R 1 and R 2 are independently hydrogen, methyl or ethyl, preferably methyl or ethyl, most preferably methyl, and n is an integer from 3 to 20, preferably from 4 to 15, most preferably 5 to 10 is.

The monomer solution or suspension preferably contains 0.005 to 1 wt .-%, particularly preferably from 0.02 to 0.5 wt .-%, most preferably from 0.05 to 0.2 wt .-% of ethylenically unsaturated, ionic surfactant, based in each case on the unneutralized monomer a).

The present invention is based on the recognition that even small amounts of increase e- thylenisch unsaturated, ionic surfactants, the swell rate (FSR) significantly. Characterized that the ethylenically unsaturated, ionic surfactants are incorporated into the polymer network, their influence on the surface tension of the aqueous extract is low.

The amount of ethylenically unsaturated, ionic surfactant is customarily selected such that the surface tension of the aqueous extract preferably at least 55 mN / m, more preferably at least 60 mN / m, most preferably at least 65 mN / m, is.

The reason for this is that when using the present invention to be employed ethylenically unsaturated, nonionic surfactants while the surface tension of the aqueous extract decreases probably due to the fact that a) the conversion of the ethylenically unsaturated, nonionic surfactants is not complete and / or b) that the copolymerized ethylenically un- saturated, nonionic surfactants subsequently surfactant groups, for example when using Acrylsäureestern and methacrylic acid by ester hydrolysis, split off.

The water-absorbing polymer particles are prepared by polymerizing a monomer solution or suspension, and are typically water insoluble.

The monomer a) is preferably water soluble, ie the solubility in water at 23 ° C is typically at least 1 g / 100 g water, preferably at least 5 g / 100 g water, more preferably at least 25 g / 100 g of water, most preferably at least 35 g / 100 g water.

Suitable monomers a) are for example ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and itaconic acid. Particularly preferred monomers a) are acrylic acid and methacrylic acid. Most particularly preferred is acrylic acid. Further suitable monomers a) are, for example, ethylenically unsaturated sulfonic acids such as styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS). Impurities can have a considerable influence on the polymerization. Therefore, the raw materials used should have the highest possible purity. Therefore, it is often advantageous to purify the monomers a) specifically. Suitable purification methods are, for example, in WO 2002/055469 A1, WO 2003/078378 A1 and WO 2004/035514 A1. A suitable monomer a) is, for example, according to WO 2004/035514 A1 purified acrylic acid having 99.8460 wt .-% acrylic acid, 0.0950 wt .-% acetic acid,

0.0332 wt .-% water, 0.0203 wt .-% by weight of propionic acid, 0.0001 wt .-% furfurals, 0.0001 wt .-% of maleic anhydride, 0.0003 wt .-% diacrylic acid and 0.0050. -% hydroquinone monomethyl ether.

The monomer a) typically includes polymerization inhibitors, preferably hydroquinone monoethers, as storage stabilizers.

The monomer solution comprises preferably up to 250 ppm by weight, preferably at most 130 ppm by weight, particularly preferably at most 70 ppm by weight, preferably at least 10 ppm by weight, particularly preferably at least 30 ppm by weight, especially around 50 wt . ppm, hydro- chinonhalbether, based in each case on the unneutralized monomer a). For example, an ethylenically unsaturated acid-functional monomer may be used with an appropriate content of hydroquinone to prepare the monomer solution.

Preferred hydroquinone monoethers are hydroquinone monomethyl ether (MEHQ) and / or alpha-tocopherol (vitamin E).

Suitable crosslinkers b) are compounds having at least two groups suitable for crosslinking. Such groups are for example ethylenically unsaturated groups which can be free-radically interpolymerized into the polymer chain and functional groups which can form a) covalent bonds with the acid groups of the monomers. Also suitable are polyvalent metal salts which can form coordinate bonds with at least two acid groups of the monomer a), suitable crosslinkers b).

Crosslinkers b) are preferably compounds having at least two polymerizable groups which can be free-radically interpolymerized into the polymer network. Suitable crosslinkers b) are, for example, ethylene glycol dimethacrylate, diethylene glycol diacrylate, Polyethylenglykoldi- acrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallylammonium chloride, tetraallyloxyethane as described in EP 0530438 A1, di- and triacrylates as described in EP 0547847 A1, EP 0559476 described A1, EP 0632068 A1, WO 93/21237 A1, WO 2003/104299 A1, WO 2003/104300 A1, WO 2003/104301 A1 and DE 103 31 450 A1, mixed te acrylamide, the more well as acrylate ethylenically unsaturated contain groups as described in DE 103 31 456 A1 and DE 103 55 401 A1, or crosslinker mixtures as beispiels-, in DE 195 43 368 A1, DE 196 46 484 A1, WO 90/15830 A1 and WO 2002/032962 A2 describes , Preferred crosslinkers b) are pentaerythritol triallyl ether, tetraallyloxyethane, rylamid Methylenbismethac-, 15-tuply ethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, triallylamine, and tetra allyl ammonium chloride. Very particularly preferred crosslinkers b) are the acrylic acid or methacrylic acid to di- or triacrylates esterified multiply ethoxylated and / or propoxylated glycerols as described for example in WO 2003/104301 A1. Particularly advantageous are di- and / or triacrylates of 3- to 10-tuply ethoxylated glycerol. Very particular preference is given to di- or triacrylates of 1 - to 5-tuply ethoxylated and / or propoxylated glycerol. On master- th preferred are the triacrylates of 3- to 5-tuply ethoxylated and / or propoxylated glycerol, especially the triacrylate of 3-tuply ethoxylated glycerol.

The amount of crosslinker b) is preferably 0.05 to 1, 5 wt .-%, particularly preferably 0.1 to 1 wt .-%, most preferably 0.2 to 0.5 wt .-%, each based on the un- neutralized monomer a). With increasing crosslinker content, the Zentrifugenretentionskapa- decreases capacity (CRC) and the absorption under a pressure of 21, 0 g / cm 2 (AUL0.3 psi) passes through a maximum.

The initiators c) all -Create radicals under the polymerization de compounds can be used, for example, thermal initiators, redox initiators, photoinitiators. Suitable redox initiators are sodium peroxodisulfate / ascorbic acid, water peroxide / ascorbic acid, sodium peroxodisulfate / sodium bisulfite and Wasserstoffpero- hydroxide / sodium bisulfite. Preferably, mixtures of thermal initiators and redox initiators are used, such as sodium / hydrogen peroxide / ascorbic acid. As reducing component is but is preferably a mixture of the disodium salt of 2- hydroxy-2-sulfinatoacetic acid, (the disodium salt of 2-hydroxy-2-sulfonatoacetic acid and sodium bisulfite available as Brüggolit® FF6 and FF7 Brüggolit® from Bruggemann Chemicals; Heilbronn; DE) or the disodium salt of 2-hydroxy-2-sulfinatoacetic acid available in pure form (as Blancolen® HP from Bruggemann Chemicals; Heilbronn, DE), are used.

With the ethylenically unsaturated, acid groups-bearing monomers a) copolymerizable ethylenically unsaturated monomers d), acrylamide, methacrylamide, hydroxy ethyl acrylate are, for example, hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, Dimethylaminoethylacry- methacrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate.

As water-soluble polymers e) include polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives, modified cellulose, such as methylcellulose or hydroxyethylcellulose, gelatin, polyglycols or polyacrylic acids, preferably starch, starch derivatives and modified cellulose are set once. Typically, an aqueous monomer solution is used. The water content of the monomer solution is preferably from 40 to 75 wt .-%, particularly preferably from 45 to 70% by weight, most preferably from 50 to 65 wt .-%. It is also possible Monomersuspensio- NEN, ie monomer solutions with excess monomer a), for example sodium use. With increasing water content, the energy consumption increases in the subsequent drying and, with falling water content, the heat of polymerization can only be removed inadequately.

The preferred polymerization inhibitors require dissolved erstoff for optimum effect sow. Therefore, the monomer solution before the polymerization by inertization, ie flowing through with an inert gas, preferably nitrogen or carbon dioxide, be freed of dissolved oxygen. Preferably, the oxygen content of the monomer before the polymerization to less than 1 ppm by weight, particularly preferably to less than 0.5 ppm by weight, very particularly preferably lowered to less than 0.1 ppm by weight.

Suitable reactors are, for example, kneading or belt reactors. In the kneader, the resulting in the polymerization of an aqueous monomer solution or suspension is polyvinyl lymergel comminuted continuously by, for example, in opposite stirring shafts, as described in WO 2001/038402 A1. The polymerization on the belt is described for example in DE 38 25 366 A1 and US 6,241, 928th In the polymerization in a belt reactor a polymer gel which has to be comminuted in a further process step, for example in an extruder or kneader is produced.

For improving the drying properties of the decomposed kleinerte polymer gel obtained by means of a kneader, can also be extruded.

but it is also possible to aqueous monomer to dropletize and to polymerize the droplets obtained in a heated carrier gas stream. Here, the process steps of polymerization and drying can be combined, as described in WO 2008/040715 A2, WO 2008/052971 A1 and WO 1/026876 201 A1.

The acid groups of the polymer gels are typically partly neutralized. The neutralization is preferably carried out at the stage of the monomers. This is usually done by mixing in the neutralizing agent as an aqueous solution or forthcoming is also given to as a solid. The degree of neutralization is preferably from 25 to 95 mol%, particularly preferably from 30 to 80 mol%, very particularly preferably from 40 to 75 mol%, for which the customary neutralizing agents can be used, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or alkali metal hydrogencarbonates and mixtures thereof. Instead of alkali metal salts and ammonium salts can be used. Sodium and potassium are particularly preferred as alkali metals, but very particular preference is given to sodium hydroxide, sodium carbonate or sodium hydrogen carbonate and mixtures thereof. However, it is also possible for the neutralization after the polymerization carried out at the stage of forming in the polymerization the polymer gel. Furthermore, it is possible up to 40 mol%, preferably 10 to 30 mol%, particularly preferably 15 to 25 mol%, to neutralize the acid groups before polymerization by already added to a portion of the neutralizing agent to the monomer solution and the desired final degree of neutralization only after the polymerization at the stage of the polymer gel is set. When the polymer gel at least partially neutralized after the polymerization, the polymer gel is preferably comminuted mechanically, for example by means of an extruder, wherein the neutralizing agent is sprayed on, sprinkled or poured on and then be carefully mixed. The gel mass obtained can be repeatedly extruded for homogenization.

The polymer gel is then preferably with a belt dryer dried until the residual moisture content is preferably 0.5 to 15 wt .-%, particularly preferably 1 to 10 wt .-%, most preferably 2 to 8 wt .-%, by weight, wherein the residual moisture content in accordance with recommended by the EDA NA test method no. WSP 230.2-05 "Mass loss Upon Heating" is determined. At too high a residual moisture content, the dried polymer gel has too low a glass transition temperature T g and is difficult to process further. At too low a residual moisture content of the dried polymer gel is too brittle, and in the subsequent comminution steps, undesirably large amounts of polymer particles with too small a particle size ( "fines") in. The solids content of the gel before the drying is preferably from 25 to 90 wt .-% , more preferably from 35 to 70 wt .-%, most preferably from 40 to 60 wt .-%. Alternatively, a fluidized bed dryer or a paddle dryer for the drying may be used. The dried polymer is then ground and classified, useful grinding commonly single or multi-roll mills, preferably two- or three-stage roll mills, pin mills, hammer mills or vibratory mills are used.

The average particle size of the separated fraction as a product polymer particles is preferably at least 200 upstream μηη, particularly preferably μηη from 250 to 600, especially from 300 to 500 μηη. The average particle size of the product fraction can be found in "Particle Size Distribution" by the EDANA recommended test method No. WSP 220.2-05., The mass of the screen fractions are plotted in cumulated form and the mean particle size is determined graphically. The mean particle size here is the value of the mesh size which gives rise to a cumulative 50 wt .-%.

The proportion of particles having a particle size of at least 150 μηη is preferably at least 90 wt .-%, particularly preferably at least 95 wt .-%, most preferably at least 98 wt .-%.

Polymer particles with too small a particle size lower the permeability (SFC). Therefore, the content should be ( "fines") be low for small polymer particles. Too small polymer particles are therefore typically removed and recycled into the process. This is preferably done before, during or immediately after polymerization, that is, before the drying of the polymer gel. The too small polymer particles can be wetted with water and / or aqueous surfactant before or during the recirculation.

It is also possible in later process steps to separate excessively small polymer particles, for example, after the surface or another coating step. In this case, the recycled are surface to small polymer particles or otherwise coated, for example with fumed silica.

When a kneading reactor used for polymerization, the small polymer particles are preferably added during the last third of the polymerization.

If the added very late excessively small polymer particles, for example, only in a downstream of the polymerization reactor, for example, an extruder, then the excessively small polymer particles can become difficult to incorporate into the resulting polymer. Insufficiently incorporated, excessively small polymer particles dissolve during the grinding process again, are from the dried polymer in classifying therefore removed again and increase the amount of excessively small polymer particles.

The proportion of particles μηη with a particle size of at most 850, is preferably at least 90 wt .-%, particularly preferably at least 95 wt .-%, most preferably at least 98 wt .-%. The proportion of particles μηη with a particle size of at most 600, is preferably at least 90 wt .-%, particularly preferably at least 95 wt .-%, most preferably at least 98 wt .-%.

Polymer particles with too large particle size lower the swell rate. The proportion of excessively large polymer particles should also be low.

Excessively large polymer particles are therefore typically removed and recycled into the grinding of the dried polymer gel. The polymer particles may be surface to further improve the properties. Suitable surface postcrosslinkers are compounds containing groups which can form covalent bonds with at least two carboxylate groups of the polymer particles. Suitable compounds are, for example, polyfunctional amines, polyfunctional amidoamines, polyfunctional epoxides, as described in EP 0083022 A2, EP 0543303 A1 and EP 0937736 A2, di- or polyfunctional alcohols as described in DE 33 14 019 A1, DE 35 described 23 617 A1 and EP 0450922 A2, or .beta.-hydroxyalkylamides such as in DE 102 04 938 A1 and US 6,239,230 described. Further, in DE 40 20 780 C1 cyclic carbonates, by DE 198 07 502 A1 2- oxazolidinone and its derivatives, such as 2-hydroxyethyl-2-oxazolidinone, in DE 198 07 992 C1 bis- and poly-2-oxazolidinones, in DE 198 54 573 A1 2-oxotetrahydro-1, 3-oxazine and its derivatives, by DE 198 54 574 A1 N-acyl-2-oxazolidinones, DE 102 04 937 A1 cyclic ureas, in DE 103 34 584 A1 bicyclic Amidoacetale, in EP 1199327 A2 oxetanes and cyclic ureas and 2003/031482 A1 morpholine-2,3-dione and its derivatives as described in WO suitable surface postcrosslinkers.

Preferred surface are ethylene carbonate, ethylene glycol diglycidyl ether, conversion reduction products of polyamides with epichlorohydrin and mixtures of propylene glycol and 1, 4-butanediol.

Very particularly preferred surface postcrosslinkers are 2-hydroxyethyl-2-oxazolidinone, 2-oxazolidinone and 1, 3-propanediol.

Furthermore, surface postcrosslinkers which comprise additional polymerizable ethylenically unsaturated groups as described in DE 37 13 601 A1

The amount of surface postcrosslinker is preferably from 0.001 to 5 wt .-%, particularly preferably 0.02 to 2 wt .-%, most preferably from 0.05 to 1 wt .-%, each based on the polymer particles.

In a preferred embodiment of the present invention before, during or after the surface in addition to the Oberflächennachvernetzern polyvalen- te cations on the particle surface.

The usable in the inventive method polyvalent cations include for example divalent cations such as the cations of zinc, magnesium, calcium, iron and strontium, trivalent cations such as the cations of aluminum, iron, chromium, rare earths and manganese, tetravalent cations such as the cations of titanium and zirconium. Possible counterions are hydroxide, chloride, bromide, sulfate, hydrogensulfate, carbonate, hydrogencarbonate, nitrate, phosphate, hydrogen phosphate, dihydrogen phosphate and carboxylate, such as acetate, citrate and lactate. There are also possible salts having different counter ions, for example, basic aluminum salts such as aluminum mono Aluminiummonoacetat or lactate. miniummonoacetat aluminum sulfate, aluminum lactate, and aluminum are preferred. Apart from metal salts poly- amines can be used as polyvalent cations.

The amount of polyvalent cation used is, for example, 0.001 to 1 wt .-%, preferably 0.005 to 0.5 wt .-%, particularly preferably 0.02 to 0.2 wt .-%. based in each case on the polymer particles. The surface postcrosslinking is typically performed such that a solution of the surface postcrosslinker is sprayed onto the dried polymer particles. After the spraying, the polymer particles are coated with surface thermal drying, wherein the surface postcrosslinking can take place both before and also currency rend drying.

The spraying of a solution of the surface postcrosslinker is preferably performed in mixers with moving mixing tools, such as screw mixers, disk mixers and shovel mixers. Particular preference is given to horizontal mixers such Schaufelmi- shear, very particular preference to vertical mixers. The distinction in the horizontal mixer and vertical mixer via the bearing of the mixing shaft, ie horizontal mixer having a horizontally mounted mixing shaft and vertical mixers have a vertically mounted mixing shaft. Suitable mixers Horizontal Ploughshare® mixers include for example (Gebr Lödige Maschinenbau GmbH;. Paderborn, Germany), Vrieco-Nauta continuous mixers (Ho sokawa Micron BV, Doetinchem, Netherlands), Processall® Mixmill Mixer (Processall®, Incorporated; Cincinnati; USA) and Schugi Flexomix® (Hosokawa Micron BV, Doetinchem, Netherlands). but it is also possible the surface postcrosslinker spraying in a fluidized bed. The surface postcrosslinkers are typically used as an aqueous solution. the penetration depth of the surface postcrosslinker can be adjusted in the polymer particles on the content of nonaqueous solvent and total amount of solvent.

Preferably, mixtures of solvents are used, such as isopropanol / water, 1, 3-propanediol / water and propylene glycol / water, wherein the mixing mass ratio is preferably from 20:80 to 40:60.

The thermal drying is preferably in contact dryers, more preferably paddle dryers, most preferably disk dryers. Suitable dryers are, for example, Hosokawa Bepex® horizontal paddle driers (Hosokawa Micron GmbH;

Leingarten; Germany), Hosokawa Bepex® Disc driers (Hosokawa Micron GmbH; Leingarten, Germany), Holo-Flite® dryers (Metso Minerals Industries Inc .; Danville, USA) and Nara Paddle Dryer (NARA Machinery Europe; Frechen; Germany). Moreover, fluidized bed dryers can be used.

Drying may take place in the mixer itself, by heating the jacket or blowing in warm air. Equally suitable is a downstream dryer, for example a tray dryer, a rotary tube oven or a heatable screw. Particularly advantageous is mixed in a fluid bed dryer and dried.

Preferred drying temperatures are in the range 100 to 250 ° C, preferably 120 to 220 ° C, particularly preferably 130 to 210 ° C, most preferably 150 to 200 ° C. The pre- ferred residence time at this temperature in the reaction mixer or dryer is preferably at least 10 minutes, more preferably at least 20 minutes, most preferably at least 30 minutes and usually at most 60 minutes. In a preferred embodiment of the present invention, the water-absorbing polymer particles are cooled after the thermal drying. The cooling is preferably in contact coolers, more preferably paddle coolers, disk coolers very particularly preferably carried out. Suitable coolers include, for example Hosokawa Bepex® Horizontal Paddle Cooler (Hosokawa Micron GmbH; Leingarten, Germany), Hosokawa Bepex® Disc Cooler (Hosokawa Micron GmbH; Leingarten, Germany), Holo-Flite® coolers (Metso Minerals Industries Inc .; Danville, USA ) and Nara paddle cooler (NARA Machinery Europe; Frechen; Germany). Moreover, fluidized bed coolers can be used.

In the cooler, the water absorbing polymer particles to 20 to 150 ° C, preferably 40 to 120 ° C, particularly preferably 60 to 100 ° C, most preferably 70 to 90 ° C cooled.

Subsequently, the surface polymer particles can be classified again, be excessively small and / or separated into large polymer particles and recycled to the process.

The surface postcrosslinked polymer particles can be coated or to further improve the properties moistened. The subsequent moistening is preferably carried out at 30 to 80 ° C, particularly preferably at 35 to 70 ° C, very particularly preferably at 40 to 60 ° C. At excessively low temperatures, the water-absorbing polymer particles tend to agglomerate and at higher temperatures, water already evaporates appreciably. The amount of water used for remoisturizing is preferably from 1 to 10 wt .-%, more preferably from 2 to 8 wt .-%, most preferably from 3 to 5 wt .-%, each based on the water-absorbing polymer particles. Through the subsequent moistening the mechanical stability of the polymer particles is increased, and reduces their tendency to static charge. the subsequent moistening is advantageously carried out in the cooler by thermal drying. Suitable coatings for improving the swell rate and the permeability (SFC) are, for example, inorganic inert substances, such as water-insoluble metal salts, organic polymers, cationic polymers and di- or polyvalent metal cations. Suitable coatings for dust binding are, for example, polyols. Suitable coatings against the undesired caking tendency of the polymer particles include for example fumed silica such as Aerosil® 200, and surfactants, such as Span® 20. A further object of the present invention are obtainable according to the process of this invention water-absorbing polymer particles.

The water-absorbing polymeric particles of the invention have a Zentrifugenretenti- onskapazität (CRC) of typically at least 15 g / g, preferably at least 20 g / g, preferably at least 25 g / g, more preferably at least 30 g / g, most preferably at least 35 g / g , on. The centrifuge retention capacity (CRC) of the water-absorbing polymer particles is typically less than 60 g / g. The water-absorbing polymeric particles of the invention have an absorption under a pressure of 49.2 g / cm 2 (AUL0.7 psi) of typically at least 10 g / g, preferably at least 15 g / g, preferably at least 20 g / g, more preferably at least 22 g / g, most preferably at least 23 g / g. The absorption under pressure of 49.2 g / cm 2 (AUL0.7 psi) of the water-absorbing polymer particles is typically less than 30 g / g.

The water-absorbing polymeric particles of the invention have an absorption under a pressure of 63.0 g / cm 2 (AUL0.9 psi) of typically at least 5 g / g, preferably at least 10 g / g, preferably at least 15 g / g, more preferably at least 17 g / g, most preferably at least 18 g / g. The absorption under pressure of 63.0 g / cm 2 (AUL0.9 psi) of the water-absorbing polymer particles is typically less than 30 g / g.

The water-absorbing polymeric particles of the invention have a permeability (SFC) of typically at least 50 x 10 "7 cm 3 sec / g, preferably at least 80 x 10" 7 cm 3 sec / g, preferably at least 100 x 10 "7 cm 3 s / g, more preferably at least 120 x 10 "7 cm 3 sec / g, most preferably at least 130 x 10" 7 cm 3 sec / g, (SFC) on. permeability of the water-absorbing polymer particles is typically less than 250 x 10 "7 cm 3 s /G. Another object of the present invention are sanitary articles, water-absorbing polymer particles comprising the present invention, in particular hygiene articles for feminine hygiene, hygiene products for light and heavy incontinence, diapers or small animal litter.

The production of the hygiene article is in the monograph "Modern Superabsorbent Polymer Technology", FL Buchholz and AT. Graham, Wiley-VCH, 1998, pages 252-258 describes.

The hygiene articles usually comprise a water-impermeable back side, a water-permeable top and therebetween an absorbent core of the erfindungsgemä- SEN water-absorbing polymer particles and fibers, preferably cellulose. The proportion of the water-absorbing polymer particles in the absorbent core according to the invention is preferably 20 to 100 wt .-%, preferably 50 to 100 wt .-%. methods:

The standard test methods described below, labeled "WSP" described in "Standard Test Methods for the Nonwovens Industry", 2005 edition, published jointly by the "Worldwide Strategy Partners" EDANA (Avenue Eugene Plasky 157, 1030 Brussels, Belgium ,) and INDA www.edana.org (1100 Crescent Green, Suite 1 15, Cary, North Carolina 27518, USA, www.inda.org). This publication is available both from EDANA and from INDA. The measurements should, unless otherwise specified, be carried out at an ambient temperature of 23 ± 2 ° C and a relative humidity of 50 ± 10%. the water-absorbing polymer particles are mixed thoroughly before the measurement.

moisture content

The moisture content of the water-absorbing polymer particles is determined according to the EDANA recommended test method No.. WSP 230.2-05 "Mass Loss Upon Heating".

Centrifuge Retention Capacity (Centrifuge Retention Capacity)

The centrifuge retention capacity (CRC) is determined according to the EDANA recommended test method No. WSP 241.2-05. "Fluid Retention Capacity in Saline, after Centrifugation".

Absorption under a pressure of 21, 0 g / cm 2 (absorption under load)

The absorption under a pressure of 21, 0 g / cm 2 (AUL0.3 psi) of the water-absorbing polymeric particles is determined according to the EDANA recommended test method No.. WSP 242.2-05 "Absorption under pressure, gravimetry Determination". extractable

The level of extractables of the water absorbing polymer particles is determined according to the EDANA recommended test method No.. WSP 270.2-05 "Extractable".

Swell rate (Free Swell Rate)

To determine the swell rate (FSR) 00 g (= Wi) of the water-absorbing polymer particles are 1, is weighed into a 25 ml glass beaker and evenly distributed on to the soil. Then, 20 ml of a 0.9 wt .-% saline solution are metered by means of a dispenser in a second beaker and the contents of this beaker are rapidly added to the first and a stopwatch is started. As soon as the last drop is absorbed saline, which confirmed by the disappearance of the reflection on the liquid surface, the stopwatch is stopped. The exact amount of liquid which has been poured from the second beaker and absorbed by the polymer in the first beaker is accurately determined by weighing back the second beaker

Figure imgf000015_0001
The time required for the absorption, which was measured with the stopwatch, is denoted t. The disappearance of the last drop of liquid on the surface is determined as time t.

Hence the swell rate (FSR) is calculated as follows:

Figure imgf000015_0002

However, when the moisture content of the water absorbing polymer particles is more than 3 wt .-%, the weight should be corrected for this moisture content Wi. Permeability (Saline Flow Conductivity)

(SFC) is the permeability of a swollen gel layer under pressure of 0.3 psi (2070 Pa), as described in EP 0 640 330 A1, determined as the gel layer permeability of a swollen gel layer of water-absorbing polymer particles, wherein the mentioned in above patent application that the glass frit (40) is no longer used, the plunger (39) made of the same plastic material as the cylinder (37) and now distributed uniformly over the entire contact surface was on page 19 and in Figure 8 described apparatus modified to 21 bores of equal size contains. The procedure and the evaluation of the measurement remains unchanged from EP 0 640 330 A1. The flow rate is recorded automatically.

The permeability (SFC) is calculated as follows:

SFC [cm 3 s / g] = (Fg (t = 0) xl0) / (dxAxWP), where Fg (t = 0) is the flow of NaCl solution in g / s is obtained from a linear regression analysis of the Fg (t) of flow determinations by extrapolation to t = 0, L0 is the thickness of the gel layer in cm, d the density of the NaCl solution in g / cm 3, A is the area of the gel layer in cm 2, and WP the hydrostatic pressure over the gel layer in dyn / cm 2.

Surface tension of the aqueous extract

There is added 0.50 g of the water absorbing polymer particles is weighed into a small beaker and mixed with 40 ml of a 0.9 wt .-% saline solution was added. The contents of the beaker are stirred at 500 U / min for 3 minutes with a magnetic stirring bar, then allowed to settle for 2 minutes. Finally, the surface tension (OFS) of the supernatant aqueous phase is measured with a K10-ST digital tensiometer or a comparable apparatus having platinum plate (Krüss GmbH, Hamburg, Germany). The measurement is carried out at a temperature of 23 ° C.

Examples

The following copolymerizable monomers were used:

Sipomer® PAM-100 (Rhodia Operations, Aubervilliers, France), a Polyethylenglykolmo- nomethacrylat Phosphatester with a molecular weight of about 400 Daltons.

Sipomer® PAM-200 (Rhodia Operations, Aubervilliers, France), a Phosphatester a Polypropylenglykolmonomethacrylats with a molecular weight of about 500 Daltons. Sipomer® PAM-300 (Rhodia Operations, Aubervilliers, France), a Phosphatester a polypropyleneglycol monoacrylate having a molecular weight of about 500 Daltons.

Sipomer® PAM-4000 (Rhodia Operations, Aubervilliers, France), a Phosphatester a hydroxyethyl methacrylate.

Adeka Reasoap® SR-10 (ADEKA Europe GmbH, Dusseldorf, Germany), the ammonium salt of a poly (oxy-1, 2-ethanediyl) -a-sulfo-co- [1 - (hydroxymethyl) -2- (2-propenyloxy) ethoxy] - Cio / Ci4-alkyl ether. Measuring the surface tension

There were 1, 03 g of the test substance at 1, 00 I demineralized water, dissolved at 23 ° C. 40 ml of this solution was weighed into a small beaker. The contents of the beaker was stirred at 500 rev / min for 3 minutes with a magnetic stir bar. (Hamburg; Germany Krüss GmbH) Finally, the surface tension of the supernatant aqueous phase with a digital tensiometer type K10-ST was. The measurement was carried out at a temperature of 23 ° C.

Substance surface tension

[MN / m]

deionized water 72.0

Span® 20 50.8

Sipomer® PAM 100 71 2

Sipomer® PAM 200 63.5

Sipomer® PAM 300 60.4

Sipomer® PAM 71 4000, 2

Adeka Reasoap® SR-10 65.0

NaAMPS *) 72.3

MPEGMA ") 70.0

*) Sodium salt of 2-acrylamido-2-methylpropane

* *) Methoxy polyethylene glycol-2000-methacrylate production of base polymers:

Example 1 (Comparative Example)

A kneader with two sigma-waves from model LUK 8.0 K2 (Coperion Werner & Pfleiderer GmbH & Co. KG, Stuttgart, Germany) was flushed with nitrogen for inerting and then with a liberated by bubbling nitrogen from oxygen mixture of 4786.99 g of a 37.3 wt .-% sodium acrylate solution, 514.45 g of acrylic acid and 522.95 g deionized water filled initial. Subsequently, 6.9 g of 3-tuply ethoxylated glycerol triacrylate (ca. 85 wt .-%) are dissolved in 100.0 g of acrylic acid as an internal crosslinker and, subsequently, as the initiator 1 1, 89 g of a 15 wt .-% aqueous sodium persulfate solution and 1, 32 g of a 3 wt .-% aqueous hydrogen peroxide solution added. Subsequently, 19.82 g of a 0.5 wt .-% aqueous ascorbic acid solution were added. The extruder was operated at speeds of 96 revolutions per minute on one shaft and me 48 rpm on the other shaft. Immediately after the addition of ascorbic acid solution by passing the heating liquid (80 ° C) was heated through the heating jacket of the kneader. Once the temperature in the compounder not increase the heating was stopped and the polymer gel kneaded for a further 13 minutes. Subsequently, the gel was cooled to about 63 ° C and then removed from the kneader. The gel was divided in portions of 1080 g evenly on grid trays and dried in a convection oven at 175 ° C for 90 min. Subsequently, the dried gel was milled on a roll mill from the model LRC 125/70 (Bauermeister Zerkleinerungstechnik GmbH, Norderstedt, Germany) eluting sequentially gap widths of 1000 μηη, 600 μηη and were adjusted μηη 400th The water-absorbing polymer particles were sieved and the sieve fractions thus obtained mixed that the following particle size distribution was obtained:> 710 μηι 0 wt .-%

600-710 μηι 13.3 wt .-%

500-600 μηι 23.3 wt .-%

300-500 μηι 43.6 wt .-%

150-300 μηι 19.8 wt .-%

<150 μηι 0 wt .-%.

The resulting mixture is homogenized in a 5 I metal vessel in a Röhnrad-type mixer RRM ELTE 650 ST (J. Engelsmann AG, Ludwigshafen, Germany).

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A.

example 2

Example 1 was repeated. There were dissolved 0.10 g of Adeka addition Reasoap® SR-10 in the monomer solution.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A.

example 3

Example 1 was repeated. There were dissolved 0.20 g of Adeka nomerlösung addition Reasoap® SR-10 in the Mo.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A. example 4

Example 1 was repeated. There were dissolved 0.50 g of Adeka addition Reasoap® SR-10 in the monomer solution.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A. example 5

Example 1 was repeated. There were an additional 1, 00 g of Adeka Reasoap® SR-10 dissolved in the monomer solution.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A.

Example 6 (Comparative Example)

Example 1 was repeated. There were additionally dissolved 2.00 g Sipomer® PAM 100 in the monomer.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A.

example 7

Example 1 was repeated. There were an additional 1, 00 g Sipomer® PAM 200 dissolved in the monomer solution.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A. example 8

Example 1 was repeated. There were additionally dissolved 2.00 g Sipomer® PAM 200 in the monomer. The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A.

Example 9 Example 1 was repeated. There were additionally dissolved 3.00 g Sipomer® PAM 200 in the monomer.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A. example 10

Example 1 was repeated. There were additionally dissolved 4.00 g Sipomer® PAM 200 in the monomer.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A.

Example 1 1 Example 1 was repeated. There were additionally dissolved 10.00 g Sipomer® PAM 200 in the monomer.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A.

example 12

Example 1 was repeated. There were additionally 1 dissolved 00 g Sipomer® PAM 300 in the monomer solution.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A.

example 13

Example 1 was repeated. There were additionally dissolved 2.00 g Sipomer® PAM 300 in the monomer.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A.

example 14

Example 1 was repeated. There were dissolved 2.00 g of additional Sipomer® PAM 4000 in the monomer solution.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A. Example 15 (Comparative Example)

Example 1 was repeated. It was further 2.00 g of methoxy polyethylene glycol 2000 methacrylate (MPEGMA) dissolved in the monomer solution.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A.

Example 16 (Comparative Example)

Example 1 was repeated. There were dissolved, in addition 2.00 g of the sodium salt of 2-acrylamido-2-methylpropane sulfonic acid (NaAMPS) in the monomer solution.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A.

Example 17 (Comparative Example)

Example 1 was repeated. only 425.93 g of deionized water were initially charged to the reactor and 99 g of a 2 wt .-% aqueous solution were added, degassed with nitrogen solution of Sorbitanmonododecanoat (Span® 20) to the initiator solution in place of 522.95 g deionized water.

The resulting water-absorbing polymer particles were analyzed. The results are summarized in Table A.

Table A: Summary of base polymers.

Figure imgf000022_0001

Comparative example

no comonomer

Oberflachennachvernetzung in the presence of an additional surfactant: Example 18 (Comparative Example)

1200 g of the base polymer of Example 1 were used to Oberflachennachvernetzung in a ploughshare ® mixer with heating jacket type M5 (Gebr. Lödige Maschinenbau GmbH, Paderborn, Germany) at 23 ° C and a shaft speed of 200 revolutions per minute by means of a two-substance spray nozzle following solution-coated (based on the base polymer):

0.992 wt .-% isopropanol

0.14 wt .-% of a solution of 50 wt .-% 1, 3-propanediol

and 50 wt .-% of N- (2-hydroxyethyl) -2-oxazolidinone

0.248 wt .-% deionized water

0.70 wt .-% 1, 2-propanediol

0.50 wt .-% of a 22 wt .-% aqueous aluminum lactate solution

0.20 wt .-% of a 2 wt .-% aqueous solution of sorbitan After spraying, the shaft speed was reduced to 50 revolutions per minute, and the product by raising the temperature of the heating jacket (temperature of the heating fluid 238 ° C) to a product temperature brought from 185 ° C. To the reaction mixture, 10 samples each of about 20g, starting with the product reaching the temperature of 185 ° C taken in sum, every 5 minutes. The samples were allowed to cool and each at 23 ° C μηη sieved at 710, wherein the fraction <710 μηη used.

The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table B.

example 19

Example 18 was repeated with 1200 g of the base polymer of Example 3. FIG.

The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table B. example 20

Example 18 was repeated with 1200 g of the base polymer of Example 4. FIG.

The obtained oberflachennachvernetzten absorbing polymer particles were lysed analogous. The results of the comparable samples with a CRC about 27 g / g are summarized in Table B.

Example 21 Example 18 was repeated with 1200 g of the base polymer of Example 5. Fig.

The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table B.

Example 22 (Comparative Example)

Example 18 was repeated with 1200 g of the base polymer of Example 6. Fig. The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table B. example 23

Example 18 was repeated with 1200 g of the base polymer of Example 8. FIG.

The resulting surface postcrosslinked water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table B. example 24

Example 18 was repeated with 1200 g of the base polymer of Example. 13

The resulting surface postcrosslinked water-absorbing polymer particles were lysed analogous. The results of the comparable samples with a CRC about 27 g / g are summarized in Table B.

Table B Summary of the polymers according to Oberflachennachvernetzung with additional surfactant.

Figure imgf000024_0001

*) Comparative example

The results show that the surfactant monomers (FSR) significantly increase the swell rate, while reducing the surface tension.

With Sipomer® PAM 200, the best results were obtained, that is, a high swell rate and only a slight reduction of surface tension. Maybe surfactant groups can be removed from the polymer by hydrolysis. In this case, the less sensitive to hydrolysis methacrylate (as Sipomer® PAM 200) superior to less hydrolysis Acrylsäureestern (such Sipomer® PAM 300). Furthermore, a sufficient reactivity of the monomer used is important. To assign allyl ethers (such as Adeka Reasorp® SR-10) to a significantly lower reactivity, so that the water absorbing polymer particles produced therewith also contain unreacted monomer.

Surface postcrosslinking in the absence of an additional surfactant: Example 25 (Comparative Example)

1200 g of the base polymer of Example 1 were used for surface postcrosslinking in a ploughshare ® mixer with heating jacket type M5 (Gebr. Lödige Maschinenbau GmbH, Paderborn, Germany) at 23 ° C and a shaft speed of 200 revolutions per minute by means of a two-substance spray nozzle following solution-coated (based on the base polymer):

0.992 wt .-% isopropanol

0.14 wt .-% of a solution of 50 wt .-% 1, 3-propanediol

and 50 wt .-% of N- (2-hydroxyethyl) -2-oxazolidinone

0.448 wt .-% deionized water

0.70 wt .-% 1, 2-propanediol

0.50 wt .-% of a 22 wt .-% aqueous aluminum lactate solution After spraying, the shaft speed was reduced to 50 revolutions per minute, and the product by raising the temperature of the heating jacket (temperature of the heating fluid 238 ° C) to a product temperature of 185 brought ° C. To the reaction mixture, 10 samples each of about 20g, starting with the product reaching the temperature of 185 ° C taken in sum, every 5 minutes. The samples were allowed to cool to 23 ° C each can be bought and μηη sieved at 710, wherein the fraction <710 μηη used.

The resulting surface postcrosslinked water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C.

example 26

Example 25 was repeated with 1200 g of the base polymer of Example 2. FIG. The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C. example 27

Example 25 was repeated with 1200 g of the base polymer of Example 3. FIG.

The obtained oberflachennachvernetzten absorbing polymer particles were lysed analogous. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C.

Example 28 Example 25 was repeated with 1200 g of the base polymer of Example 5. Fig.

The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C.

Example 29 (Comparative Example)

Example 25 was repeated with 1200 g of the base polymer of Example 6. FIG. The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C.

example 30

Example 25 was repeated with 1200 g of the base polymer of Example 7. FIG.

The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C.

example 31

Example 25 was repeated with 1200 g of the base polymer of Example 8. FIG. The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C. example 32

Example 25 was repeated with 1200 g of the base polymer from Example 9th

The obtained oberflachennachvernetzten absorbing polymer particles were lysed analogous. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C.

Example 33 Example 25 was repeated with 1200 g of the base polymer of Example 10. FIG.

The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C.

example 34

Example 25 was repeated with 1200 g of the base polymer from Example 1 1st The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C.

Example 35 (Comparative Example)

Example 25 was repeated with 1200 g of the base polymer of Example fourteenth

The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C.

example 36

Example 25 was repeated with 1200 g of the base polymer of Example 12. Fig. The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C. example 37

Example 25 was repeated with 1200 g of the base polymer of Example. 13

The obtained oberflachennachvernetzten absorbing polymer particles were lysed analogous. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C.

Example 38 (comparative example) Example 25 was repeated with 1200 g of the base polymer of Example 15 °.

The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C.

Example 39 (Comparative Example)

Example 25 was repeated with 1200 g of the base polymer from Example 16th The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C.

Example 40 (Comparative Example)

Example 25 was repeated with 1200 g of the base polymer of Example 17th

The obtained oberflachennachvernetzten water-absorbing polymer particles were analyzed. The results of the comparable samples with a CRC about 27 g / g are summarized in Table C. Table C. Summary of the polymers by surface postcrosslinking without additional surfactant.

Figure imgf000029_0001
*) Comparative example

* *) No comonomer

The results also show that the surfactant monomers (FSR) significantly increase the swell, while reducing the surface tension.

The comonomers not the invention (as MPEGMA and NaAMPS) have only a minor impact, both on the swell rate (FSR) and on the surface tension. Not polymerized surfactants (such as Span® 20) lower the surface tension too much.

Claims

claims
1 . A process for producing water-absorbing polymer particles by polymerizing a monomer solution or suspension comprising a) at least one ethylenically unsaturated monomer bearing acid groups, which may be at least partially neutralized,
b) at least one crosslinker,
c) at least one initiator,
d) optionally one or more copolymerizable with the above-mentioned under a) monomers ethylenically unsaturated monomers and
e) optionally one or more water-soluble polymers, characterized in that the monomer solution or suspension comprising at least one e- thylenisch unsaturated ionic surfactant.
2. The method according to claim 1, characterized in that the ethylenically unsaturated ionic surfactant is an anionic surfactant.
3. The method according to claim 2, characterized in that the anionic group is a phosphate or a sulfate group.
4. The method according to any one of claims 1 to 3, characterized in that the apolar group is a polypropylene glycol group in the ethylenically unsaturated ionic surfactant.
5. The method according to any one of claims 1 to 4, characterized in that the ethylenically unsaturated group lether- an allyl the ethylenically unsaturated, nonionic surfactant, vinyl ether, acrylic ester or methacrylic ester group.
6. The method according to any one of claims 1 to 5, characterized in that the ethylenically unsaturated, ionic surfactant is a compound of general formula (I)
Figure imgf000030_0001
wherein R 1 and R 2 are independently hydrogen, methyl or ethyl and n is an integer from 3 to 20..
7. The method according to any one of claims 1 to 6, characterized in that the monomer solution or suspension, based on the unneutralized monomer a), from 0.05 to 0.2 wt .-% of ethylenically unsaturated, nonionic surfactant contains.
8. A method according to any one of claims 1 to 7, characterized in that the monomer a) is acrylic acid mol% to than 90.
9. The method according to any one of claims 1 to 8, characterized in that the monomer a) is neutralized to 30 to 80 mol%.
10. The method according to any one of claims 1 to 9, characterized in that the monomer solution or suspension based on the unneutralized monomer a) is from 0.1 to 1 wt .-% of the crosslinking agent b).
1. 1 Water-absorbing polymer beads preparable according to a process of claims 1 to 10 degrees.
12. A hygiene article comprising water-absorbing polymeric particles according to claim 1. 1
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WO2014079694A1 (en) 2012-11-21 2014-05-30 Basf Se A process for producing surface-postcrosslinked water-absorbent polymer particles
WO2014118024A1 (en) * 2013-01-29 2014-08-07 Basf Se Method for producing water-absorbing polymer particles with high swelling rate and high centrifuge retention capacity with simultaneously high permeability of the swollen gel bed
WO2015028158A1 (en) 2013-08-26 2015-03-05 Basf Se Fluid-absorbent article
WO2015046604A1 (en) 2013-09-30 2015-04-02 株式会社日本触媒 Granular water-absorbent filling method and granular water-absorbent sampling method
EP2739660B1 (en) 2011-11-17 2015-07-29 Evonik Degussa GmbH Super-absorbing polymers with rapid absorption properties and method for producing the same
WO2018141677A1 (en) 2017-02-06 2018-08-09 Basf Se Fluid-absorbent article

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